Method of controlling pests with biosurfactant penetrants as carriers for active agents

ABSTRACT

A penetrating composition can include an active agent that has an activity that is either beneficial for plants or controls pests. The composition can also include a penetrant that is present in an effective amount for carrying the at least one active agent into or through a medium, the medium being at least one of a plant, soil, or pest. Also, penetrating composition can be used for increasing the permeation of an active agent in an animal. The composition includes an active agent having an activity that is beneficial for an animal. Also, the composition includes a penetrant selected from the group consisting of biosurfactants, glycolipids, lipopeptides, favolipids, lipoproteins, phospholipids, lipopolysaccharide-protein complexes, polysaccharide-protein-fatty acid complexes, and combinations thereof. A biosurfactant composition can include an effective amount of a biosurfactant for controlling a pest, preserving a plant cutting, or reducing effects of environmental stress on a plant.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation of U.S. patent application Ser. No. 11/209,132, filed on Aug. 22, 2005, which is a continuation-in-part of U.S. patent application Ser. No. 11/141,669, filed on May 31, 2005, which claims the benefit of U.S. Provisional Patent Application Ser. No. 60/575,913, filed Jun. 1, 2004, and benefit of U.S. Provisional Patent Application Ser. No. 60/604,139, filed Aug. 23, 2004, which patent applications are all incorporated herein by specific reference in their entirety.

BACKGROUND OF THE INVENTION

1. The Field of the Invention

The present invention relates to formulations that include a penetrant. More particularly, the present invention relates to formulations, which can be solid, liquid, or paste, and methods of using the same for introducing active substances into plants, humans, animals, and/or pests.

2. The Relevant Technology

Although chemical pesticides are valuable for pest control, their use poses many problems. They tend to harm non-target organisms such as humans, domestic animals, beneficial insects, and wildlife. In addition, their residues tend to remain on the crop and may accumulate in the soil, water, or air. Another concern is the development pesticide resistance by the targeted organisms. Due to the serious environmental problems associated with chemical pesticides, the demand for safer pesticides and alternate pest control strategies is increasing.

Similarly, conventional compositions that are used for applying, distributing, or introducing active substances (e.g., insecticides, herbicides, nutrients, minerals, or medicinal drugs) into pests, insects, humans, plants, and animals, suffer from some of the same problems. In addition, many such compositions and compounds are expensive, difficult to handle, or are otherwise unsuitable for some applications. Many compounds that are suitable for use with, for example, crops, are not appropriate for use with humans or animals. For these reasons, much of the cost of delivering active agents relates to the costs associated with the carriers.

Therefore, it would be advantageous to have compositions including penetrants that can safely and effectively deliver active substances.

SUMMARY OF THE INVENTION

Generally, embodiments of the present invention include a homogeneous penetrating composition that can be used for increasing the permeation of an active agent through a medium. Such a penetrating composition can include at least one active agent. The activity of the active agent can be beneficial for plants; or for controlling pests. The composition also includes at least one penetrant that is present in an effective amount for carrying the at least one active agent into or through a medium. While the penetrant can carry the active agent through a wide range of mediums, the preferable mediums are plants, such as trees, soil, or the pest's environment or habitat. As such, the penetrant with or without an additional active agent can be used to control pests such as insects, larvae, insect eggs, mites, algae, moss, mold, slime, nematodes, bacteria, fungi, amoeba, mollusks, and the like.

Additionally, the penetrant can be selected from aliphatic sulfones, acyclic sulfones, sulfones, sulfoxides, biosurfactants, glycolipids, lipopeptides, favolipids, polyvinylpyrrolidone, lipoproteins, phospholipids, lipopolysaccharide-protein complexes, polysaccharide-protein-fatty acid complexes, penetration enhancers, and combinations thereof. The active agent can be selected from the group consisting of pesticides, elicitors, biopesticides, biopesticide byproducts, alkaloids, plant-growth regulators, plant nutrients, mineral, seed treatment agents, preserving agents, disinfectants, sterilizers, surfactants, soil conditioners, baits, dyes, plant stress-reducing agents, and combinations thereof.

The penetrating composition can also include a solubility controlling agent, which can either slow the release of the active agent from the composition or increase the solubility of the active agent within the composition. The solubility controlling agent can be selected from the group consisting of slow release cross-linked swellable gel, slow release cross-linked swellable polyacrylamide gel, wax, chitin, chitosan, C12-C20 fatty acid, myristic acid, stearic acid, palmitic acid, C12-C20 alcohol lauryl alcohol, cetyl alcohol, myristyl alcohol, stearyl alcohol, amphiphilic esters of fatty acids, glycerol, monoester C12-C20 fatty acids, glyceryl monolaurate, glyceryl monopalmitate, glycerol esters of fatty acids, polyethylene monostearate, polypropylenemonopalmitate glycols, C12-C20 amines, lauryl amine, mystyl amine, stearyl amine, amide C12-C20 fatty acids, and combinations thereof.

Moreover, the penetrant can form a complex with the active agent, wherein the complex can be a chelate. The complexing penetrant can preferably be selected from glycolipids, lipopeptides, favolipids, lipoproteins, phospholipids, lipopolysaccharide-protein complexes, and polysaccharide-protein-fatty acid complexes. Additionally, the complexed active agent can preferably be selected from a plant nutrient, mineral, imidacloprid, acephate, phosphite salt, natural oil, and combinations thereof.

Additionally, the penetrating composition can be used for improving the health of a tree. As such, a method for increasing the health of a tree can include drilling a hole into the tree, the hole being at an angle that is not congruent with a radii of the tree and being substantially parallel with soil from which the tree grows. That is, the hole is not aligned or substantially aligned with the radii, but can intersect the radii at any possible angle. After the hole is formed, the composition is then applied into the hole in the tree.

The composition can also be used for controlling pests, wherein controlling a pest is considered to include killing, disabling, or immobilizing a pests or otherwise rendering the pests substantially incapable of causing harm. As such, the method of controlling the pests can be performed by applying the composition to the pest directly or indirectly. Indirect application of the composition can be included in applying the composition to the environment to which the pest lives, such as to a host plants, mounds, soil, surfaces, dwellings, cracks, and the like. This can include applications to human dwellings, office buildings, schools, kitchens, bathrooms, bathtubs, and the like. Additionally, when an animal is infected with a pests, such as those described herein, the animal can be treated by spraying, coating, applying, dipping, or other process of applying the composition to the animal. Also, when controlling the pest, it can be preferable that the active agent is a pesticide and/or the penetrant is a biosurfactant. Optionally, the pesticide is complexed with the biosurfactant.

Additionally, the composition can be used for retaining moisture in a plant. This can be done by applying the composition to the plant, wherein the penetrant and/or active agent is a biosurfactant. As such, the composition can be applied to any portion of the plant, including leaves, stem, trunk, flowers, roots, and the like. Also, the composition can be used to preserve plant cuttings, wherein a plant cutting is a plant that have been cultivated by being cut from the soil. The composition can preserve the plant cutting by being applied to the plant before or after being cut. Optionally, this can also preserve the flowers that may be present on a plant cutting, wherein the composition can be applied directly to the flowers, leaves, stem, or cutting site.

In one embodiment, the present invention includes a composition for increasing the permeation of an active agent in a mammal. Such a composition includes at least one active agent that has an activity that is beneficial for an animal, wherein the animal can include humans or other well-known animals. Also, the composition includes at least one penetrant selected from the group consisting of biosurfactants, glycolipids, lipopeptides, favolipids, lipoproteins, phospholipids, lipopolysaccharide-protein complexes, polysaccharide-protein-fatty acid complexes, and combinations thereof. Preferred active agents for animals include minerals, nutrients, vitamins, drugs, cancer drugs, and combinations thereof. Optionally, the active agent is complexed with the penetrant, which can be in the form of a chelate.

In one embodiment, the present invention includes a biosurfactant composition. The biosurfactant composition can include an effective amount of a biosurfactant for performing a beneficial function. The beneficial function can be one of the following: controlling a pest; preserving a plant cutting; or reducing effects of environmental stress on a plant. Preferably, the biosurfactant is selected from the group consisting of glycolipids, lipoproteins, flavolipids, lipoproteins, phospholipids, lipopolysaccharide-protein complexes, polysaccharide-protein-fatty acid complexes, and combinations thereof. Additionally, the further comprises a solubility controlling agent selected from the group consisting of slow release cross-linked swellable gel, slow release cross-linked swellable polyacrylamide gel, aliphatic compound, wax, chitin, chitosan, C12-C20 fatty acid, myristic acid, stearic acid, palmitic acid, C12-C20 alcohol lauryl alcohol, cetyl alcohol, myristyl alcohol, stearyl alcohol, amphiphilic esters of fatty acids, glycerol, monoester C12-C20 fatty acids, glyceryl monolaurate, glyceryl monopalmitate, glycerol esters of fatty acids, polyethylene monostearate, polypropylenemonopalmitate glycols, C12-C20 amines, lauryl amine, mystyl amine, stearyl amine, amide C12-C20 fatty acids, and combinations thereof.

In the instance the biosurfactant composition is used for controlling pests, the composition further comprises at least one active agent in an effective amount for controlling pests, the at least one active agent being selected from the group consisting of pesticides, insecticides, sterilants, disinfectants, miticides, fungicides, bactericides, viricides, mollucides, nematicides, algicides, herbicides, and combinations thereof. Also, the method of controlling the pests can include applying the biosurfactant composition to a pest. This can include being applied to the environment in which the pests lives, such as an ant mound, to protect plants, soils, aquatic systems, ponds, homes, or structures such as kitchens, bathrooms, or bathtub surfaces. As such, the active agent along with the penetrant can be applied when in the form of a gel, solid capsule, or tablets, especially for ant mound treatments.

In the instance the biosurfactant composition is used for reducing effects of environmental stress on a plant the composition can be applied to any portion of the plant. This can also include applying the biosurfactant composition to the soil surrounding or proximate to the plant. Also, the bio surfactantcomposition can be used to preserve a plant that has been cultivated by being cut. As such, the composition can be applied to a plant before or after being cut, such as contacting the biosurfactant to the site where the plant was cut. Optionally, a plant cutting that includes a flower can be preserved, which can include applying the biosurfactant to the flower.

Additionally, the biosurfactant composition can be configured to have a slow rate of release, which may be a zero-order kinetic rate of release. In any event, by including a solubility controlling agent in the biosurfactant composition, the rate at which the biosurfactant is released from the composition can be controlled and at a slower rate. As such, applying the biosurfactant composition to a medium can slowly release the biosurfactant to penetrate the medium, wherein the medium is at least one of a plant or pest. While the solubility controlling agent can be any of such agents described herein, it is preferable that the agent is a cross-linked swellable polyacrylamide gel.

BRIEF DESCRIPTION OF THE DRAWINGS

To further clarify the advantages and features of the present invention, a more particular description of the invention will be rendered by reference to specific embodiments thereof which are illustrated in the appended drawings. It is appreciated that these drawings depict only typical embodiments of the invention and are therefore not to be considered limiting of its scope. The invention will be described and explained with additional specificity and detail through the use of the accompanying drawings in which:

FIG. 1 illustrates examples of six different structure of rhamnose lipids R1, R2, R3, F4, A and B of Pseudomonas aeruginosa;

FIG. 2A illustrates a prior art method of embedding a capsule, such as those disclosed herein, into a tree; and

FIGS. 2B-2C illustrate a novel method of embedding a capsule, such as those disclosed herein, into a tree.

DETAILED DESCRIPTION OF EMBODIMENTS OF THE INVENTION

Generally, embodiments of the present invention relate to compositions that can be used for treating plants and methods of using the same. The compositions include at least one penetrant or carrier and at least one active substance, e.g., pesticides. The penetrant can be used as a carrier of active substances to enhance the solubility, complexation, permeability, wettability and/or translocation of active substances to and within plants, seeds, and into soils and pests. Optionally, the compositions may also include one or more solubility controlling agents and additives.

Penetrating compounds can be used for treating trees in order to obtain many desirable results. In part, the benefits can be due to the ability of the dissolved solution to penetrate deeply and efficiently into the treated body, and to penetrate the conductive vascular tissue, the non-conductive tissues, and heartwood of the tree. Consequently, fewer holes may need to be drilled around the tree perimeter. The ability to treat trees, while drilling fewer holes than those that generally have been required in conventional treatments, is highly advantageous because it can minimize the risks of infections that may occur from decay, adverse organisms, or secondary infections by insects.

In one embodiment of the invention, formulations are prepared to include penetrants configured to be absorbed into seeds, trees, plants, pests, soils, and the like. As such, these penetrant-containing formulations can be used in applications to treat seeds, plants, pests and soils as described herein and in the incorporated references.

In another embodiment of the invention, formulations are prepared to enhance penetration and increase the radial and tangential flow of active agents through the treated plant. It can be preferable to use semi-solid or solid preparations for tree injections or soil applications. This can be especially important to enhance the lateral and radial diffusion and/or penetration of the injection material.

In another embodiment of the invention, aliphatic and acyclic sulfones can be used as carriers and penetrants in tree and/or plant treatment formulations. Examples of the sulfones are Methylsulfonylmethane (MSM), ethyl sulfone, butadiene sulfone. MSM can be preferable in some applications because of the many advantages that are explained in more detail below. Thus, the aliphatic and acyclic sulfones can be used as a carrier, adjuvant, surfactant, and/or penetrant for active substances.

Additionally, formulations using MSM and other sulfones may be used for applications to treat seeds, plants, pests and soils. Accordingly, the formulations can be prepared as solid, semi-solid, powders, gels, pastes, liquids, and the like. Moreover, MSM and/or the other sulfones may be used as a matrix base for different types of formulations (solid, semi-solid, paste, gel, cream, or liquid). For example, a solid pesticidal tablet, which includes MSM or other sulfone can be a carrier or penetrant.

Methylsulfonylmethane is a chemical with many favorable characteristics. It is a natural, safe, inexpensive, small molecule, and is stable at high temperatures with a melting point (mp) of 109° C., and boiling point (bp₇₆₀) of 238° C. Its non-hygroscopic nature, solvent action, and moderate melting point make it ideal for solid preparations such as tablets. Merck's Index describes it as being a high temperature solvent for many inorganic and organic compounds. Additionally, the other sulfones have similar favorable characteristics.

Research and data show that MSM and/or other sulfones can be effective penetrants with many useful functions, such as permeability, wetting agent, mobility, and a translocation enhancer of many active substances through dead or live tissues of plants and pests, and can be a very effective solubilizer of substances. MSM and/or other sulfones have many advantages over the well-known penetrants used in the pharmaceutical industry. In addition to the favorable characteristics mentioned above, MSM has a low molecular weight, non-toxicity, and/or in a solid state at room temperature, which is ideal for use in solid formulations as a carrier, translocation enhancer, and/or a stabilizer in formulations.

MSM can be a good binding agent for tabletting. As such, it can be used as a sole carrier and excipient in tabletting and molding. Its ideal melting point of 109° C. makes it an excellent carrier and solvent for water insoluble substances and active agents, (e.g., pesticides). Its binding ability without the addition of excipients makes it a good carrier of heat sensitive active substances in tabletting formulations. Additionally, testing MSM in tree injections at a 100% concentration did not induce any toxicity or necrosis for the treated plants. Thus, MSM and/or other sulfones can be valuable in treating plants without inducing toxicity or necrosis.

In another embodiment of the invention, biosurfactants can be used as carriers and penetrants of active agents, such as insecticides, herbicides, nutrients and minerals, medicinal drugs for humans and animals, and on the like. Microbial biosurfactants are compounds produced by variety of microorganisms such as bacteria, fungi, and yeast. Biosurfactants include low-molecular-weight glycolipids (GLs), lipopeptides (LPs), flavolipids (FLs), and high-molecular-weight polymers such as lipoproteins, lipopolysaccharide-protein complexes, and polysaccharide-protein-fatty acid complexes. Glycolipids, flavolipids, and lipopeptides form an important class of secondary metabolites that occur in many microorganisms such as Pseudomonas species (P. aeruginosa, P. putida, P. florescens, P. fragi, P. syringae), Flavobacterium spp., Bacillus spp. (B. subtilis, B. pumillus, B. cereus, B. licheniformis), Candida species (C. albicans, C. rugosa, C. tropicalis, C. lipolytica, C. torulopsis), Rhodococcus sp.; Arthrobacter spp., and on the like.

Biosurfactants have a great deal of structural diversity. Biogenetically, GLs, FLs, and LPs are derived from fatty acids that are linked either to sugars, organic acid, or peptides, respectively. For example, rhamnolipids are produced by different Pseudomonas bacterial strains and they constitute a subset of the glycolipids where one or two rhamnose sugars are attached to one or more fatty acids having a saturated or unsaturated alkyl chain. Some strains produce monorhamnolipid (R1) or dirhamnolipid (R2), others produce a mixture of R1 and R2 or different structural homologs of rhamnolipids, and some strains do not produce rhamnolipids. There are at least six forms of rhamnolipids described in the literature. A single form or a mixture of the different forms of rhamnolipids may be used to achieve the objectives of the invention.

FIG. 1 depicts six different rhamnolipids, which can be used in accordance with the present invention. R1 is an alpha-L rhamnopyranosyl-Beta-hydroxydeconyl-Beta-hydroxydecanoate. R2 is a 2-O-alpha-L-rhamnopyranosyl-alpha-L-rhamnopyranosyl-Beta.

FIG. 1 illustrates examples of different structures of rhamnose lipids. The rhamnose lipid “R1” is an alpha-L-rhamnopyranosyl-beta-hydroxydeconyl-beta-hydroxydecanoate. The rhamnose lipid “R2” is a 2-O-alpha-L-rhamnopyranosyl-alpha-L-rhamnopyranosyl-beta-hydroxydeconyl-beta-hydroxydecanoate. The rhamnose lipid “R3” is an alpha-L-rhamnopyranosyl-beta-hydroxydeconic acid. The rhamnose lipid “R4” is a 2-O-alpha-L-rhamnopyranosyl-alpha-L-rhamnopyranosyl-beta-hydroxydecanoic acid. The rhamnose lipid “A” is a 2-O-alpha-decenoyl-alpha-L-rhamnopyranosyl-beta-hydroxydeconyl-beta-hydroxydecanoic acid. The rhamnose lipid “B” is 2-O-(2-O-alpha-decenoyl-alpha-L-rhamnopyranosyl)-alpha-L-rhamnopyrano syl-beta-hydroxydeconyl-beta-hydroxydecanoic acid. While these rhamnose lipids have been depicted and described, other rhamanose lipids can also be used in the present invention.

In one embodiment, a single biosurfactant or a mixture of different biosurfactants may be used as penetrants or carriers in a formulation that can perform the functions and achieve the results described herein. In another embodiment, the aforementioned compounds may also be synthesized by standard organic synthesis methods.

Rhamnolipids may be used as a matrix base or carrier in different types of formulations (solid, semi-solid, paste, gel, or liquid) for plant and tree treatments. Preliminary research and data show that rhamnolipids can be effective carriers through plant tissues, having many useful functions such as permeability, wetting agent, mobility, and a translocation enhancer of many active substances through plants. It is also an effective solubility-controlling agent of many substances. For instance, addition of the rhamnolipid to a water-soluble insecticide acephate formulation helps control the solubility in order to provide the insecticide at a predetermined rate. Combining the rhamnolipid with the water insoluble insecticide imidacloprid helps enhances the solubility as well as the translocation of the insecticide into the treated plant or tree. Moreover, solid and/or semisolid rhamnolipid formulations can be used as a penetrant and/or as a fungicide to treat trees for fungal diseases.

Co-pending patent application Ser. No. 11/141,669, filed May 31, 2005, is incorporated herein by reference and describes biosurfactants (e.g. GLs, FLs, and LPs etc) having a powerful biopesticidal activity against many pests and diseases that affect plants. These biosurfactants also have similar biopesticide activity against pests and diseases affecting humans and animals. The pests that can be controlled by biosurfactants include insects, insect larvae and eggs, mites, algae (e.g. seaweeds, pond algae, and the microscopic algae such as blue-green algae), microbial pests (e.g. nematodes, bacteria, fungi, amoeba, parasites, etc.), moss, slime, lichens, mold, mollusks, and plant weeds. In addition, these biosurfactants may be used to treat human diseases such as ova-parasites, cysts, athlete foot and nail fungi infections, yeast infection, and hair dandruff, and the like. Biosurfactants may also be used in human chelation therapy and reduction of heavy metal toxicity. This makes these biosurfactants very effective carriers, penetrants, and biopesticides, with a wide range of beneficial uses. For example, rhamnolipids have been shown to be effective against dandruff, and as spermicidal agent.

In another embodiment, MSM or dimethyl sulfoxide (DMSO) is combined with a biosurfactant (e.g., rhamnolipid) to enhance the permeability and translocation of the carried active agents, (e.g., dyes or insecticides). Consequently, the effectiveness of the carried compound or active agent, as well as the fungicidal activity of the rhamnolipid is enhanced. It is thought, without being bound thereto, that a synergistic effect may exist between some combinations of the foregoing compounds. Tests of pesticidal formulations using high amounts of DMSO in solid or semisolid preparations show no toxicity or necrotic symptoms on the treated plants. The use of DMSO enhances penetration and effectiveness of the active agents such as insecticides.

Another advantage of using rhamnolipids, MSM, and/or DMSO as a carrier in plant and tree treatments is their antimicrobial activity. This can be very beneficial in tree injection applications where the method of application causes injury to the roots or the trunk. Many wood-decay and rot causing organisms can be found in soil or on tree trunks. These harmful organisms may propagate and grow at the injection site and within the vascular tissue of the treated tree. This may block the vascular system and cause the eventual death of the treated tree. Rhamnolipids, MSM, and/or DMSO have biocidal activities that can be used in tree injection formulations in order to inhibit the growth of many adverse organisms. This is essential for the treated plant to have a fast recovery and can eliminate the need of disinfecting the drill bit with alcohol or flame after each treatment.

Additionally, antimicrobial agents such as fungicides, bactericides, and preservatives may be included in formulations where the penetrant has no antimicrobial activity. This may be beneficial for some tree injection applications. Of course, the antimicrobial agents could be used with penetrants that have antimicrobial activity.

In another embodiment of the invention, biosurfactants glycolipids, flavolipids, and/or lipopeptides can be used as complexing/chelating agent and/or delivery agents for plant nutrients. Treatment of nutrient deficiencies can be greatly advanced by a method that not only solubilizes metals but also facilitates the introduction of these metals across the wall/membrane barriers. The use of metal delivery agents can be a beneficial method of treatment to combat nutrient deficiencies in plants, but it also can be the most challenging for three reasons: (1) the metal of interest has to be encapsulated or chelated within the delivery agent; (2) the metal complexes must penetrate a large number of plant cells and/or the hydrophobic leaf cuticle; and (3) the metal and/or delivery agents must be safe to the plant and the environment over the time of treatment. Accordingly, the following qualities of the present invention help to address these issues.

It has been shown that encapsulation of active agents with glycolipids such as rhamnolipids have enhanced stability constants over other organic acids. This is probably due to the fact that these biomolecules chelate or complex with metals more efficiently through the carboxyl group on the fatty acid moiety and the hydroxyl groups on the rhamnose. However, encapsulation and solubility alone may not be sufficient criteria for improved bioavailability, but penetration can improve bioavailability. A neutral metal-ligand complex that has an enhanced binding affinity towards the cell membrane through the hydrophobic fatty acid moiety can facilitate fusion with the cell membrane. This allows the complex to enter the cell via endocytosis. After endosomal release, the metal becomes readily available within the cytoplasm. Additionally, glycolipids, flavolipids, and/or lipopeptides are biological molecules that are environmentally safe, unlike many other synthetic chelating agents.

In another embodiment, the present invention is readily adaptable to a more general modular delivery system, where each modular component can provide a key step of metal delivery into plants. Such an approach can have two major components: (1) a chelating moiety to help chelate the metal ions; and (2) a lipid moiety to enhance absorption. The end result can be a system that chelates metals and penetrates through the cellular barriers to achieve the ultimate treatment for metal deficiency. As described herein, GLs, FLs and LPs can serve as carriers for various nutrients across the membranes of plant cells or leaf tissues.

In one embodiment, the penetrants and carriers of the present invention can increase the solubility of various agents to enable increase homogenous distribution throughout the treated plants and soils. Also, the penetrants and carriers can protect the metal from antagonists present in nature and from changes in the pH, which provides for much greater stability. The enhanced absorption of the metal-GL, metal-FL and/or metal-LP complexes can be more absorbable than the inorganic or un-complexed form of the metal. This is the result of two synergetic effects: (a) the ligand neutralizes the charge of the inorganic metal, and (b) the ligand serves as a permeation agent through its hydrophobic fatty acid moiety. The present invention can also reduce the interaction and binding of the chelated metal with adverse antagonists, which improves uptake and decreases elimination, so as to provide improved utilization. Moreover, the formulations have improved safety towards plants and the environment by being totally natural.

Of particular interest is a new class of flavolipids biosurfactants that feature citric acid as a polar moiety. Flavolipids, like other microbial-produced surfactants, exist in different forms or structural homologs. There are at least thirty-seven known flavolipid homologs produced by flavobacterium genus (Bodour et al. 2004). Flavolipids are very likely to exhibit a higher stability constant with some metals (e.g., iron) due to being similar with the iron chelators arthrobactin and aerobactin. Due to the many different biosurfactant types and structural homologs, the choice of the biosurfactant-metal complex can be determined based on the stability constant of the complex. Thus, different ratios of the biosurfactants to the nutrients may be used.

As a result, the present invention employs biosurfactants, such as glycolipids, flavolipids, lipopeptides, and the like, as well as a mixture thereof as nutrients complexing/delivery agents to maintain the nutrients in a soluble, usable form for the plant. Preliminary tests using mono- and di-rhamnolipids provide stable complexes with different nutrients such as Zn, Fe, Cu, NH₄, Ca, and K. The use of rhamnolipid in formulations containing iron can inhibit the oxidation of iron to the unavailable oxide forms, and eliminates staining associated with iron fertilizers, especially for the home and garden market For example, derivatives of the foregoing compounds or biosurfactants having similar characteristics, having a non-polar moiety (hydrophobic), having a polar moiety (hydrophilic), and/or being able to complex, solubilize or enhance the uptake of active agents (e.g., plant nutrients and insecticides) may also be employed.

In another embodiment of the invention, biosurfactants may be used as solubility controlling agents for active compounds. Biosurfactants may also be used to coat plant fertilizers, such as urea, ammonium nitrate, potassium nitrate, ammonium phosphate, ferrous sulfate, and the like, and reduce their solubility and transformation in the soil. The antimicrobial activity of some biosurfactants such as rhamnolipids may inhibit the activity of many degrading microorganisms and may reduce the transformation rate of the treated fertilizer. The addition of other solubility controlling agents described in this invention (e.g., C12-C20 fatty acids) to the formulations may also be desired. In addition to coating active agents, the presence of the biosurfactant in the formulations can aid in penetration and complexation of the carried agents.

In one embodiment of the invention, GLs, FLs, and/or LPs plant nutrient compositions may be applied to the plants or soil in solution, solid, and semi-solid compositions and in different shapes and forms. An alternate method of application involves adding the GLs, FLs, or LPs, which can be with or without plant nutrients, to the soil or the growing media (e.g., hydroponics, potting soil mix, soil-less medium) where crops are grown or to be grown. The added GLs, FLs, and LPs can solubilize and complex nutrients that are in the soil and make them available to the plants. However, it is preferable to use the pre-formulated biosurfactant-nutrient complex as described herein. The GLs, FLs, and/or LPs can be used as soil penetrants to maintain nutrients in solution and enhance their uptake by the plants. In this embodiment, soil structure may be improved, and the cation exchange capacity (CEC) of the soil may be raised. Enhancement of CEC is very beneficial for sandy soils (e.g., golf courses) to maintain the nutrients in the root zone and to reduce pollution, waste, and leaching of nutrients.

GLs, FLs, and/or LPs producing organisms (e.g., rhamnolipids producing Pseudomonas spp.) can be added to the soil or the growing media. These organisms can grow and produce the biosurfactants that complex and make nutrients available for the growing plants. The produced biosurfactants may also help the active agents penetrate through the roots. The cultures may be mixed with growth enhancement substances, such as oils, sugar or other compounds, to aid in their growth.

In another embodiment of the invention, the GLs, FLs, LPs or a mixture as penetrants and complexing agents can be added to pre-formulated fertilizer products (chelated and non-chelated) to enhance nutrients uptake.

In another embodiment of the invention, the GLs, FLs, LPs, and/or mixture thereof may be combined with other chelating agents (synthetic or natural) used in the fields of plant, human, or animal nutrition. In one embodiment, natural chelating agents are used. Although not necessary, a chelating agent is used that has metal-conditional stability constant similar to or less than the conditional stability constant of GLs-FLs, or LPs-metal complexes. The presence of the GLs, FLs, or LPs in the composition can help in the penetration of the complexed nutrients as described in the invention.

Using GLs, FLs or LPs as complexing agents for nutrients may also be beneficial for foliar application. In minute amounts (100 ppm or less), biosurfactants have a natural tendency to lower the surface tension of the applied mixture, which reduces or eliminates the need for adding surfactants before spraying plant leaves. In general, foliar application of agrochemicals active agents can be associated with quick dryness on the leaf surface and poor uptake of the active agents. Salt accumulation on the leaf surface is sometimes noticeable within few minutes of foliar application. The presence of the fatty acid moiety in the biosurfactants maintains the applied active agents with or without a matrix in a hydrated form for a longer period of time and effectively improves the uptake and permeability of the carried active agents through the leaf. Preliminary results show that the uptake of the active agent was directly related with the concentration of the biosurfactant. At biosurfactant concentrations of about 500 ppm and above, the uptake of the carried active agents, especially nutrients, is greatly increased.

The presence of the lipid moiety in the biosurfactants acts as a barrier or insulator on the leaves and may aid in maintaining the cells hydrated. This helps reduce moisture loss and evapo-transpiration from the sprayed leaves, this can have the potential of reducing water consumption in the treated plants to aid in conserving water. Furthermore, the biosurfactants can be used for the prevention and protection of treated plants against environmental stress conditions such as drought and frost.

In another embodiment, flavolipids can be used as a source of organic nitrogen as a nutrient to supply plants with this nutrient. Also, the biosurfactants can be used as preservatives for flower and plant cuttings.

Other penetrants that may be used in the invention are penetrants used in the pharmaceutical industry as tissue softening agents, as carriers of medicaments, and as gene transfer agents. Examples of penetration enhancers include: alcohols, such as ethanol, isopropanol, and methanol; polyols, such as n-alkanols, myoinositol, pinitol, limonene, terpenes, dioxolane, propylene glycol, ethylene glycol, and glycerol; acyclic polyols such as mannitol, sorbitol, and xylitol; alkyl methyl sulfoxides, such as decylmethyl sulfoxide, dimethyl sulfoxide, tetradecyl methyl sulfoxide; esters, such as isopropyl myristate/palmitate, ethyl acetate, butyl acetate, methyl propionate, capric/caprylic triglycerides; ketones; amides, such as sulfamides, acetamides, acetamide oleates; various surfactants, such as sodium lauryl sulfate, quaternary ammonium salts, lecithins, cephalins, alkylbetamines; various alkanoic acids such as caprylic acid; lactam compounds, such as laurocapram; alkanols, such as cetyl alcohol, oleyl alcohol, stearyl alcohol; and miscellaneous compounds as dimethyl acetamide, dimethyl formamide, and N,N-diethyl-m-toluamide, tetrahydrofurfuryl alcohol, dialkylamino acetates, and pyrrolidones (2-pyrrolidone, N-methyl-2-pyrrolidone, N-(2-Hydroxyethyl) pyrrolidone, and sorbitan. Another set of penetrating agents used in the pharmaceutical industry are gene transfer agents that introduce genes and active compounds through the cell membrane. Typically, these agents modify the charge on the membrane, and thereby allow the charged molecule to enter through the membrane. Example of these gene transfer agent are: bile salts, poly(acids), poly(bases), glycerophosphates or their salts, steroidal polyamines, and the like.

Combinations of the liquid penetrants glycerol, propylene glycol, and DMSO with additives or gelling agents such as polysaccharides (starch, cellulose), chitin, pectin, alginate salts, polyethylene glycol, or stearate derivatives, may be formulated to make solid or semi-solid formulations such as gel, paste, spikes, blocks, tablets, or rods for soil, root, or trunk application. While being used as carriers in tree injection treatments, the physical state of penetrants may be liquid, solid, or semi-solid. Penetrants may also have solvent action. Additionally, poly(acids), poly(bases), or glycerophosphates can be made in a paste form. For example, combining Poly(lactide) with calcium salts forms semi-solid preparation that can change into solid.

Additionally, the solubilizing agent ethanolamines such as tri-ethanolamine and its salts (sulfates, phosphates, salicylates, and HCl) are also effective penetrants through wood and plant tissues. These may be used to make solid or liquid preparations that can be used as carriers for active agents, especially for tree injection compositions.

Accordingly, there are no specific limitations as to the kind of penetrant to be used, as long as it is capable of carrying active agents, and if necessary, solubilize the active agents to be easily absorbed or translocated by plant tissues. If necessary, a solvent may be added to the penetrating agent to help in the solubilization of hard-to-dissolve compounds in a certain penetrant. For example, mannitol, sorbitol, ammonium ion, and/or urea have some penetration capability, but limited solvent activity. The addition of a solubilizer, such as polyethylene gylcol or polyethylene oxide, may enhance their activity.

In tree injection applications, naturally solid penetrants may be used, and/or penetrants may be prepared in solid or semi-solid (e.g., gel, paste, cream) formulations using carriers and penetrants with solvent action and having a low molecular weight. The presence of a penetrant-solvent in the semisolid or solid formulations is helpful in delaying the formation of a callus layer (resin) at the site of the treatment injection. Many trees, such as conifers, peaches, and apricots, tend to produce and accumulate excessive resin after injury. The solid tree injection formulations of the present invention having penetrants DMSO, MSM, rhamnolipids, and/or triethanolamine can delay the accumulation of resin till the formulation is substantially dissolved and used by the treated plant.

Additionally, the penetrating agent can enhance the permeability of the carried active component through treated plant roots. By placing the treatment compound next to the root, permeability is significantly improved and better uptake of the active component by the plants is achieved. Better uptake of the active component by plants with the aid of a penetrant reduces the possibility of waste and minimizes contaminating the environment. By increasing absorption efficiency and translocation in the plants, soil fixation or leaching of the active compounds is reduced.

Treating an individual plant through root flares and/or trunk injections can enable the penetrating agent to improve vertical, horizontal, and/or radial penetration, as well as the tangential flow of the carried material. As such, better distribution of the active compound in the treated plant can be achieved. In the case of treating against borer insects, better penetration and distribution of the active agent can be essential for the success of the overall therapy. This is especially important for the insecticidal treatment against borers (e.g., Aspen borers) that tunnel deeply into the heartwood of the stem, where the activity of the vascular tree sap is minimal and the treating agent has minimal access. The presence of a penetrant, such as DMSO, MSM, and/or triethanolamine, in the insecticidal formulation can facilitate the penetration of the insecticide toward the heartwood of the treated trunk and significantly increases the success rate of borers control.

In the instance of treating trees, it is not necessary to drill holes and inject the formulations at equally spaced intervals around the circumference of the tree. Instead, the presence of a penetrant helps the injected material flow horizontally and vertically through the trunk and root flares. Due to the increase in the horizontal and/or vertical flow, the same size tree may be treated with fewer injections than would otherwise be needed. Fewer injections mean fewer holes need to be drilled and, advantageously, at wider spacing intervals between the injections. Depending on the amount of material that is injected, the lateral movement can ultimately lead to the development of a complete ring of the injected material diffusing through the trunk.

In one embodiment, the penetrants and carriers of the present invention can be used to treat seeds. As such, a penetrant may also be incorporated with seed treatment agents. The formulations can be mixed with the seeds, or incorporated into seed coating formulations.

In another embodiment, a controlled release formulation can be prepared to include a matrix of the penetrant and/or carrier having an active compound dissolved or dispersed therein This allows the active compound to be released over time. As such, it is possible to achieve superior control over the dissolution rate of the solid or semi-solid compositions so they can be used in a variety of applications. This can be especially essential for root flare or trunk injection techniques in order to control the release rate of the active agent, and/or to enhance the radial and lateral flow of injected material. Enhancement of lateral and radial transport can provide effective distribution of the active agents, and fewer holes may need to be drilled around the tree. Controlled release formulas may be used for compounds that are phyto-toxic for plants and also to be used for formulations having active agents with short half-lifes.

A controlled release matrix can be formed from a composition including a carrier with or without a penetrant and a solubility control agent. Solubility control agents may include amphiphilic compounds having a hydrophilic portion and a hydrophobic portion, which are usually located at opposite ends of the molecule. The presence of hydrophobic portions in the solubility control agent can slow down the rate at which the matrix is dissolved or eroded when in contact with tree sap or a liquid environment. The use of a large amount of hydrophobic component in the formulation can greatly retard solubility of the formulation. Therefore, the release kinetics of the active ingredient can be determined by the properties of the matrix components. In addition, the shape of the formulation may affect solubility. Accordingly, varying the size and shape of the formulation as well as the proportion of the solubility—controlling agent can control the rate of dissolution. Also, the process of formulation may affect the solubility of the matrix. For instance, the pressure applied by a tablet press during the manufacturing process can be adjusted to determine the solubility of the dosage. Exerting more pressure produces stiffer tablets that take longer to dissolve when used to treat trees.

In another embodiment, solubility control agents or excipients may be used in the formulations to control the release of the active substances. Suitable solubility control agents may include the following: wax; chitin; chitosan; C12-C20 fatty acids such as myristic acid, stearic acid, palmitic acid; C12-C20 alcohols such as lauryl alcohol, cetyl alcohol, myristyl alcohol, and stearyl alcohol; amphiphilic esters of fatty acids with glycerol; monoesters; C12-C20 fatty acids such as glyceryl monolaurate, glyceryl monopalmitate; glycol esters of fatty acids such as polyethylene monostearate or polypropylenemonopalmitate glycols; C12-C20 amines such as lauryl amine, myristyl amine, stearyl amine; and amides C12-C20 fatty acids. Additional ingredients can be incorporated in the formulation to modify the properties of the composition and to improve the compatibility between the components.

The agro-chemically active substances that can be used in the present formulations are to be understood as all substances which are customarily used for the treatment of plants Accordingly, the agro-chemically active substances can include the following: pesticides which include insecticides, miticides, fungicides, bactericides, viricides, mollucides, nematicides, algicides, mos sicides, and herbicides; elicitors, plant activators, or substances that may enhance the defense mechanism of the plant such as acibenzolar-5-methyl, azadirachtin, phosphorous acid or phosphite salts, and the like; biopesticides such as pseudomonas spp, Bacillus thurengesis, Trichoderma spp, bacteriophages, etc; biopesticides byproducts; plants or herbal alkaloids and extracts with insecticidal activity such as garlic, pepper, tomato, neem, matrine, oxymatrine extracts, etc; plant-growth regulators such as auxins, gibberellins, cytokinins, ethephon, and chlorocholine chloride; organic and inorganic plant nutrients to provide plants with essential nutrients such as nitrogen, phosphorus, potassium, calcium, magnesium, sulfur, iron, zinc, manganese, etc; seed treatment agents; flowers and ornamental cuttings; shelf-life extending agents or preserving agents such as 8-hydroxyquinoline citrate, citric acid, sucrose, and the like; surfactants; soil conditioners; baits; florescent and non-florescent dyes for flowers and ornamental cuttings and for plants; and plant stress reducing agents such as anti-frost and drought resistant agents.

Suitable additives, which may be contained in the plant-treatment compositions can be substances customarily used for such preparations. Examples of such additives include adjuvants, surfactants, emulsifying agents, sticker, buffering agents, pH adjusting agents, fillers, plasticizers, lubricants, glidants, colorants, pigments, bittering agents, preservatives, stabilizers, and ultra-violet light resistant agents. Stiffening or hardening agents may also be incorporated to strengthen the formulations and make them strong enough to resist pressure or force in certain applications.

Examples of buffering agents include organic acids, amino acids, their salts, or a mixture thereof. Suitable buffering agents include acetate, arginine, aspartate, citrate, tartarate, malate, lactic acid, oxalate, malonate, glucoheptonate, pyruvate, galactarate, glucarate, gluconate, tartronate, glutamate, glycine, lysine, glutamine, methionine, cysteine, and a mixture thereof. Phosphoric and phosphorous acids or their salts and derivatives (polyphosphates or polyphosphites) may also be used. Synthetic buffers are suitable to be used but it is preferable to use organic and amino acids buffers. In addition to their buffering capacity, some of these listed compounds may help in the chelation or complexation of plant metals. The presence of the GLs, FLs, or LPs in the composition can help in the penetration of the complexed nutrients as described in the invention.

Methods of carrying out the therapeutic processes in accordance to the invention can provide formulations with the desired amount of the components. As such, the components are mixed with one another and heated, if desired, while being stirred or kneaded. The active compound can be incorporated into the penetrant matrix by being mixed directly in the matrix, dissolved in a molten matrix, or dispersed and mixed into the matrix. The ratio of active compound to matrix may vary within wide limits. The final product of the invention can be prepared by conventional procedures such as compression molding, tabletting, pressing, extrusion, injection molding, and preparing a solution.

Solid formulations may have different forms and shapes such as cylinders, rods, blocks, capsules, tablets, pills, pellets, strips, spikes, and/or the like. Solid formulations may also be milled, granulated, or powdered. The granulated or powdered material may be pressed into tablets or used to fill pre-manufactured gelatin capsules or shells. Solidified penetrants or complexing agents, such as MSM or glycolipids may be combined with the desired active agent, such as pesticides or nutrients. These formulations may be applied to a tree as is or reconstituted into a liquid format prior to use. Semi solid formulations can be prepared in paste, wax, suppository, gel, or cream preparations. Liquid formulations can be prepared in aqueous or any other desired solvent medium.

The formulations can be encapsulated using components known in the pharmaceutical industry. Encapsulation can protect the components from undesirable reactions and help the ingredients resist adverse conditions in the environment or the treated object or body (e.g., stomach). For human or animal applications, the formulations may be prepared in liquid, paste, ointment, suppository, capsule, tablet, or other well-known forms, and used in a way similar to drugs used in the medicinal drugs industry. Additionally, the compositions according to the invention can be applied to the plants, pests, or soil using various methods of application. Each method of application may be preferred under certain circumstances.

In one embodiment, the compositions in accordance with the invention may be used to introduce the active compounds into the soil or the target site such as an ant mound. Also, these preparations can be incorporated into the soil in the vicinity of the roots of the plants, in the form of a liquid, bait, powder, dusting, or granules. Alternatively, they are inserted in the soil as tablets, spikes, rods, or other shaped moldings. It can be more desirable to use tablets, rods, or spikes to minimize the reactivity and fixation of the active agents with soil particles. This can be important for pesticides, in particular, since their organic nature tend to be more reactive with soil particles. The action of the penetrant can help reduce pesticides-soil particle interactions by maintaining the pesticide in a soluble form to enhance penetration through root cells.

In one embodiment, the compositions can be used for treating individual trees or plants. For example, the formulations can be molded in different shapes or forms (e.g., solid, paste or gel, or liquid) and introduced into the vascular tissue of the plants. The molding can be in the form of tablets, capsules, plugs, rods, spikes, films, strips, nails, or plates. The shaped moldings can be introduced into holes pre-drilled in the plants or root flares, or they can be pushed or punched into the cambium layer.

One method of applying or using the compositions of the invention is to use dispensing devices, such as syringes, pumps or caulk guns, paste-tubes or plunger tubes for delivering semi-solid formulations (e.g., paste, gel, cream), into drilled holes in tree trunks or root flares. This method may be used for formulations that may or may not include penetrants.

Also, the compositions can be applied in the form of paste, gel, coating, strip, or plaster onto the surface of the plant. In one method, a plaster or strip may have a semi-solid formulation with the insecticide being placed on the side that will contact the tree, bush, or rose during the treatment. The same strip may have glue or adhesive at one or both ends to wrap around or stick to the subject being treated. Alternatively, the active agent can be combined with the adhesive over any portion of the strip.

The compositions can also be sprayed or dusted on the leaves in the form of pellets, spray solution, granules, or dust. Ingredients concentrations in the sprayable or dusting, as well as the formulations application rate may be varied widely depending on the active agents used and/or the plants being treated.

The solid or semi-solid compositions can be coated onto tablets using film-coating compounds well-known in the pharmaceutical industry such as polyethylene glycol, gelatin, sorbitol, gum, sugar, or polyvinyl alcohol. This is particularly useful for tablets or capsules having pesticide formulations. A film coating can protect the handler from coming in direct contact with the active ingredient in the formulations. In addition, a bittering agent, such as denatonium benzoate or quassin may also be incorporated in the pesticidal formulations, the coating or both. The compositions can also be powdered for being pressed tablets or filled into pre-manufactured gelatin capsules.

Additionally, the formulations may also be used to supply nutrients for the beneficial microorganisms used in agriculture or those present in the rhizosphere area of the growing crops. Essential nutrients such as cobalt and vanadium may be complexed by the biosurfactants or the penetrants and made available for these beneficial microorganisms.

The penetrants and/or compositions may also be applied on the soil surface to enhance water permeability and nutrients availability, as well as to improve soil structure. The penetrant alone without active agents may also be used for the mentioned purposes. The compositions may be applied by being injected through an irrigation system. As such, the penetrants in the invention can be used to enhance the penetration of water, active agents, or both into seeds, plant cuttings, trees, and soils. Improved water penetration using penetrants is beneficial for seed germination and for nutrient distribution in the soil and plants.

The penetrants may also be added to pre-formulated pesticidal preparations that are used as tree treatment agents. This is especially useful for formulations used in the tree injection industry (trunk or root flare injections). It can also assist in increasing the effectiveness of the herbicide in herbicidal formulations.

In another embodiment, penetrants can be used in bait formulations or pheromone traps to enhance the effectiveness of the active agent and to improve penetration through the pest. This is particularly beneficial for insecticides, pheromone traps, ant baits, and in mollusk or snail baits.

According to another embodiment, formulations used in the tree injection industry can be applied to enhance the distribution and translocation of the active agents. This method also reduces the number of holes drilled in the tree as compared to application methods of prior art. The new method includes drilling the holes at right angles or orthogonal to the radii of the tree and parallel to the soil surface. The holes can be bored inside the water conducting cambium tissue under the bark. The holes can be drilled in a tangential position, and the holes can be drilled at angle positions ranging between 90 degrees (for maximum contact with the cambium layer) to the radii to 160 degrees angle to the radii. As such, the injections may be done at about 90 to about 120 degree angles with respect to the radii of the tree trunk. In any event, the holes can be bored at any angle that is not congruent or aligned with the radii or substantially orthogonal to the tangent. The holes may be bored at a slightly downward position to secure the injected material in the hole.

FIG. 2A is a schematic diagram illustrating the prior art orientation of a therapeutic capsule 18 in a tree 10. As shown, in the prior art the capsule 18 is inserted into the tree 10 so that it passes through the bark 12 and into the phloem 14. Usually, the capsule 18 does not extend into the heartwood 16; however, the prior art orientation allows it to be possible for the capsule 18 to extend into the heartwood 16. In part, this is because the orientation of the capsule 18 has been aligned with the radii 22 of the tree. That is, a hole is bored into the tree 18 so as to be aligned with the radii 22 and orthogonal to the tangent 24. Accordingly, a deep enough hole or capsule 18 can be extended into the heartwood 16.

FIGS. 2B-2C are schematic diagrams illustrating embodiments of capsule 18 orientation in accordance with the present invention. As such, the capsule 18 is inserted into the outer surface 20 of the tree 10 at an angle α that is not aligned with the radii 24. Also, the capsule 18 is not at an angle β that is orthogonal with the tangent 24 because the radii 22 of a tree 10 is orthogonal to the tangent 24, wherein the sum of α and β is equal to 90 degrees. Accordingly, by inserting the capsule 18 at an angle of α or β, the contents of the capsule 18 can be delivered into the tree 18 more efficiently, as described herein.

For example, the capsule 18 can be oriented at an angle 28 a-j that is not aligned with the radii 22 or orthogonal with the tangent 24. This can include insertion angles 28, such as α or β, can be as follows: from about 5 to about 10 degrees (28 a); from about 10 to about 15 degrees (28 b); from about 15 to about 15 degrees (28 c); from about 20 to about 25 degrees (28 d); from about 20 to about 30 degrees (28 e); from about 30 to about 40 degrees (28 f); from about 40 to about 50 degrees (28 g); from about 50 to about 60 degrees (28 h), from about 60 to about 80 degrees (28 i), and from about 70 to about 85 degrees (28 j). In another embodiment, the angles 28 a-j can be representative to the downward angle that the hole and/or capsule 18 is oriented with respect to the ground, wherein an angle of 0 degrees represents a horizontal orientation and 90 degrees represents a vertical orientation.

The new method of injection can ensure that the treating agent is in direct contact with more conductive tissues or the phloem for better distribution and faster treatment. This may prevent the accumulation and loss of active ingredients in the heartwood area or the nonconductive tissues. In addition, reducing the number of holes bored in the trees minimizes the potential risk of infection by decay causing organisms or secondary infestation by insect borers at the site of injection. This method can be used for all trees but is particularly important for Dicotyledonous Angiosperm species. It is also beneficial for certain monocotylednous types of trees, such as palm, where the conductive vessels occupy 4 to 5 percent of the total tissues. This method may be employed with any type of formulations (liquid, solid, or paste) used in the tree injections industry.

For instance, liquid injections, gel injections, and solid capsules can be used in trunk tree injections for improving the health of the tree. For example, a DMSO-Imidacloprid Gel formulation can provide enhanced protection against pests when the composition is administered into the hole drilled into the tree, or simply applied to the outside of the tree.

In another embodiment, the action of pesticides can be enhanced by the use of penetrants. Penetrants enhance the activity of pesticides and improve their penetration through pests such as insects, fungi, and bacteria. This can be particularly important for tree borers, their larva and eggs, or both. An unexpected result has been achieved when MSM and DMSO were added to insecticide formulations of cyalothrin or acephate. This combination greatly improves the effectiveness of the insecticides. Tests with cyalothrin or acephate with penetrants sprayed on grasshoppers and caterpillars showed a much higher kill rate and in a shorter period of time than in the absence of penetrants. The results of the test are provided in Table 1.

TABLE 1 EFFECT OF ACEPHATE FORMULATIONS ON GRASSHOPPER SURVIVAL Acephate Treatments 0% 0.084% 0.084% + MSM 0.084% + DMSO Time (hrs) Grasshopper Survival Rate 4.25 100 100 100 75 5.5 100 100 75 75 6.5 100 100 50 50 7.5 100 75 50 50 9.25 100 75 25 25 14 100 50 0 0 24 100 25 0 0 32 100 0 0 0

Dry effervescent solid formulations can be prepared using an organic acid, such as citric acid or malic acid, and a carbonate salt (e.g., MgCO3, CaCO3) to generate carbon dioxide gas upon contacting tree sap after being injected into a tree. This may help in faster translocation of the active ingredient. The injection site may be sealed to prevent the carbon dioxide gas from escaping. The concentrations of the individual ingredients in the formulations can be varied within a relatively wide range.

Generally, the formulations can be prepared by mixing the needed amounts of the ingredients with one another in no particular order. The process may involve heating one or all the components at a desired temperature. For example, a pre-measured amount of MSM is melted in a vessel (e.g., a steam jacketted kettle) that is capable of being stirred. A temperature of about 110° C. is sufficient to melt the MSM. The bioactive agent (e.g., insecticide imidacloprid) is then added and dissolved in the molten mixture. If desired, other additives such as molding adjuvants are then added, and the mixture is thoroughly blended. Particular forms or moldings may be formed directly from the molten mixture by the procedures outlined herein or well-known in the art.

If a controlled release formulation is desired, a pre-measured amount of solubility control agent, such as stearic acid, is added as a molten liquid or as a solid to the MSM-imidacloprid mix described above. The mix may be extruded, molded, granulated, or ground into fine granules.

Another preparation procedure is accomplished by mixing all the needed ingredients together in a V-Mixer and pressed using a tablet press. For example a measured amount of polyvinyl pyrrolidone or MSM is mixed with acephate then pressed using a tablet press. If necessary, additives such as lubricants may be used in the formulation.

The following is a partial list of the active compounds that may be included in the present formulations and treatments, but does not include all the compounds that can be used in connection with the invention. Those of skill in the art, upon learning of the disclosure made herein, will recognize that the principles of the invention can be applied using other compounds.

Example of insecticidal, acaricidal and nematicides active substances include Abamectin, Acephate, Acriathrin, Alanycarb, Aldicarb, Aldocycarb, α-methrin, Amitraz, Aphidan, Avermectin, Azadiractinn, Azinphos A and M, Azocyclotin, Bacillus thuringesis, 4-bromo-2-(4-chlorophenyl)-1-(ethoxymethyl)-5-(trifluoro-methyl)-1H-pyrrolo-3-carbonitrile, Bendiocarb, Benfuracarb, Bensultap, β-cyfluthrin, Bifenthrin, Brofenprox, Bromophos, Bufencarb, Buprofezin, Butocarboxim, Butoxycarboxim, Butylpyridaben, Cadusafos, Carbaryl, Carbofuran, Carbophenothion, Carbosulphan, Cartap, Chloethocarb, Chlorethoxyfos, Chlorfenapyr, Chlorfenvinphos, Chlorfluazuron, Chlormephos, Chlorpyrifos, cis-Resmethrin, Clocythrin, Clofentezine, Cloprothrin, Cyanophos, Cyfluthrin, Cyhalothrin, Cyhexatin, Cypermethrin, Cyromazine, δ-methrin, Demeton, Diafenthiuron, Diazinon, Dichlofenthion, Dichlorvos, Dicliphos, Dicrotophos, Diethion, Diflubenzuron, Dimefox, Dimethoate, Dimethylvinphos, Dioxathion, Disulfoton, Edifenphos, Emamectin, Esfenvalerate, Ethiofencarb, Ethion, Ethofenprox, Ethoprophos, Etrimphos, Fenamiphos, Fenazaquin, Fenbutatin oxide, Fenitrothion, Fenobucarb, Fenothiocarb, Fenoxycarb, Fenpropathrin, Fenpyrad, Fenpyroximate, Fenthion, Fenvalerate, Fipronil, Fluazinam, Fluazuron, Flucycloxuron, Flucythrinate, Flufenoxuron, Flufenprox, Fluvalinate, Fonophos, Formothion, Fosthiazate, Fubfenprox, Furathiocarb, Heptenophos, Hexaflumuron, Hexythiazox, Imidacloprid, Iprobenfos, Isazophos, Isofenphos, Isoprocarb, Isoxathion, Ivermectin, X-cyhalothrin, Lufenuron, Malathion, Mecarbam, Mevinphos, Mesulfenphos, Metaldehyde, Methacrifos, Methamidophos, Methidathion, Methiocarb, Methomyl, Metolcarb, Mevinphos, Milbemectin, Monocrotophos, Morphothion, Moxidectin, Naled, Nitenpyram, Oils, Omethoate, Oxamyl, Oxydemethon-m, Oxydeprofos, Parathion, Permethrin, Phenthoate, Phorate, Phosalone, Phosmet, Phosphamidon, Phosphamidon, Phoxim, Pirimicarb, Pirimiphos, Profenophos, Promecarb, Propaphos, Propoxur, Prothiophos, Prothoate, Pymetrozin, Pyrachlophos, Pyradaphenthion, Pyresmethrin, Pyrethrum, Pyridaben, Pyrimidifen, Pyriproxifen, Quinalphos, salts of fatty acids (e.g., sodium, potassium, ammonium and the like), Salithion, Sebufos, Silaflutofen, Spinosad, Sulfotep, Sulprofos, Tebufenozide, Tebufenpyrad, Tebupirimphos, Teflubenzuron, Tefluthrin, Temephos, Terbam, Terbufos, Tetrachlorvinphos, Thiafenox, Thiamethoxam, Thiodicarb, Thiofanox, Thiometon, Thionazin, Tralomethrin, Triarathen, Triazophos, Triazuron, Trichlorfon, Triflumuron, Trimethacarb, Vamidothion, Xylylcarb, and Zetamethrin.

Examples of fungicides active agents include 2-aminobutane, 2-anilino-4-methyl-6-cyclopropyl-pyrimidine, 2′,6′-dibromo-2-methyl-4′-trifluoromethoxy-4′-trifluoromethyl-1,3-thiazole-5-carboxanilide, 2,6-dichloroN-(4-trifluoromethylbenzyl)-benzamide, (E)-2-methoxyimino-N-methyl-2-(2-phenoxyphenyl)-acetamide; 8-hydroxyquinoline sulphate; methyl (E)-2-{2-[6-(2-cyanophenoxy)-pyrimidin-4-yloxy]-phenyl}-3-methoxyacrylate, methyl (E)-methoximino-[alpha-(o-tolyloxy)-o-tolyl]-acetate, 2-phenylphenol (OPP), Aldimorph, Ampropylfos, Anilazine, Azaconazole, Azoxystrobin, Benalaxyl, Benodanil, Benomyl, Fenarimol, Triadimefon, Benodanil, Fenpropimorph, Triadimenol, Kitazin, Fosetyl, Tridemorph, Binapacryl, Biphenyl, Bitertanol, Blasticidin-S, Boscalid, Bromuconazole, Bupirimate, Buthiobate, Furalaxyl, Triforine, Carbendazim, Imazalil, Captafol, Captan, Carbendazim, carbonate salts as potassium carbonate, Carboxin, Chloroneb, Chloropicrin, Chlorothalonil, Chlozolinate, Copper compounds, Cufraneb, Cymoxanil, Cyproconazole, Cyprofuram, Dichlorophen, Diclobutrazol, Dichlofluanid, Diclomezin, Dicloran, Diethofencarb, Difenoconazole, Dimethirimol, Dimethomorph, Diniconazole, Dinocap, Diphenylamine, Dipyrithion, Ditalimfos, Dithianon, Dodine, Drazoxolon, Nuarimol, Oxycarboxin, Dodemorph, Prochloraz, Edifenphos, Epoxyconazole, Etaconazol, Ethirimol, Etridiazole, Fenarimol, Fenbuconazole, Fenfuram, Fenitropan, Fenpiclonil, Fenpropidin, Fenpropimorph, Fentin salts, Ferimzone, Fluazinam, Fludioxonil, Fluoromide, Fluquinconazole, Flusilazole, Flusulphamide, Flutolanil, Flutriafol, Folpet, Fosetyl-aluminium, Fuberidazole, Furalaxyl, Furmecyclox, Guazatine, Hexachlorobenzene, Hexaconazole, Hprodione, Hsoprothiolane, Hymexazol, imazalil, imibenconazole, iminoctadine, Iprobenfos, Kasugamycin, Mancopper, Mancozeb, Maneb, Manganese compounds, Mepanipyrim, Mepronil, Metalaxyl, Metconazole, Methasulphocarb, Methfuroxam, Metirarn, Metsulphovax, Myclobutanil, Nickel dimethyldithiocarbamate, Nitrothal-isopropyl, Nuarimol, Ofurace, natural oils, Oxadixyl, Oxamocarb, Oxycarboxin, Pefurazoate, Penconazole, Pencycuron, Phosdiphen, Phthalide Pimaricin, Piperalin, Polyoxin, Polysulphide salts, Probenazole, Prochloraz, Procymidone, Propamocarb, Propiconazole, Propineb, Pyrazophos, Pyrifenox, Pyrimethanil, Pyroquilon, Quinomethionate, Quintozene, salts of fatty acids (e.g., sodium, potassium, ammonium, and the like), Sulphur compounds, Tebucanozole, Tecloftalam, Tecnazene, Tetraconazole, Thiabendazole, Thicyofen, Thiophanate-methyl, Thiram, Tolclophos-methyl, Tolylfluanid, Triadimefon, Triadimenol, Triazoxide, Trichlamide, Tricyclazole, Tridemorph, Triflumizole, Triforin, Triticonazole, Validamycin A, Vinclozolin, Zinc compounds, Zineb, and Ziram.

Examples of bactericides include Bronopol, Dichlorophen, Nitrapyrin, Nickel dimethyldithiocarbamate, Kasugamycin, Octhilinone, Furancarboxylic acid, Oxytetracycline, Probenazole, Streptomycin, Tecloftalam, and Copper compounds.

Examples of herbicides include the following: Anilides, such as Diflufenican and Propanil; Arylcarboxylic acids, such as Dichloropicolinic acid, Dicamba and Picloram; Aryloxyalkanoic acids, such as 2,4-D, 2,4-DB, 2,4-DP, Fluoroxypyr, MCPA, MCPP and Triclopyr; Aryloxy-phenoxy-alkanoic esters, such as Diclofop-methyl, Fenoxaprop-ethyl, Fluazifop-butyl, Haloxyfop-methyl and Quizalofop-ethyl; Azinones, such as Chloridazon and Norflurazon; Carbamates, such as Chlorpropham, Desmedipham, Phenmedipham and Propham; Chloroacetanilides, such as Alachlor, Acetochlor, Butachlor, Metazachlor, Metolachlor, Pretilachlor and Propachlor; Dinitroanilines, such as Oryzalin, Pendimethalin and Trifluralin; Diphenyl Ethers, such as Acifluorfen, Bifenox, Fluoroglycofen, Fomesafen, Halosafen, Lactofen and Oxyfluorfen; Ureas, such as Chlortoluron, Diuron, Fluometuron, Isoproturon, Linuron and Methabenzthiazuron; Hydroxylamines, such as Alloxydim, Clethodim, Cycloxydim, Sethoxydim and Tralkoxydim; Imidazolinones, such as Imazethapyr, Imazamethabenz, Imazapyr and Imazaquin; Nitriles, such as Bromxynil, Dichlobenil and loxynil; Oxyacetamides, such as Mefenacet; Sulfonylureas, such as Amidosulfuron, Bensulfuron-methyl, Chlorimuron-ethyl, Chlorsulfuron, Cinosulfuron, Metsulfuron-methyl, Nicosulfuron, Primisulfeuron, Pyrazosulfuron-ethyl, Thifensulfuron-methyl, Triasulfuron and Tribenuron-methyl; Thiolcarbamates, such as Butylate, Cycloate, Diallate, EPTC, Esprocarb, Molinate, Prosulfocarb, Thiobencarb and Triallate; Triazines, such as Atrazine, Cyanazine, Simazine, Simetryne, Terbutryne and Terbutylazin; triazinones, such as Hexazinone, Metamitron and Metribuzin; and others, such as Aminotriazole, Beefuresate, Bentazon, Cinmethylin, Clomazone, Clopyralid, Difenzoquat, Dithiopyr, Ethofumesate, Fluorochloridone, Gibberellic acid, Glufosinate, Glyphosate, Isoxaben, Pyridate, Quinchlorac, Quinmerac, Sulphosate, Tridiphane, Dalapon, Glyphosine, loxynil, Chlorfluorenol, Dichlorprop, Dichlofop, Mecoprop, Chlormequat, Diquat, Paraquat, Chloroacetic acid, Fluazifop, Pyridate, Chlorsulfuron, Flurenol, Sulfometuron, and natural oils.

Examples of plant nutrients include those that are customary inorganic or organic fertilizers for providing plants with macro- and/or micronutrients. The methods of treatment involving the foregoing penetrants and the complexing agents are applicable to a broad range of plant nutrients including nitrogen, phosphorus, sulfur, and the metals boron, calcium, cobalt, copper, iron, magnesium, manganese, molybdenum, nickel, potassium, and zinc, or a mixture thereof. A list of representative metal salts includes acetates, bicarbonates, carbonates, chlorides, hydroxides, nitrates, oxides, phosphates, and sulfates or a mixture thereof.

Examples of plant growth regulators that can be used include Gibberilic acid, cytokinins, zeatin, auxins, naphthalene acetic acid, chlorocholine chloride and ethephon.

Additional active agents that may be used are disinfectants or sterilizers customarily used in residential areas, hospitals, storage structures, and the like. A partial list includes quaternary ammonium compounds (e.g., n-alkyl-dimethylbenzyl ammonium chloride, n-alkyldimethylethylbenzyl ammonium chloride, didecyl dimethyl ammonium chloride), bromonitroalkanols, peroxyacetic acid, glutaraldehyde, or combinations thereof.

The invention contemplates a broad range of penetrants, complexing agents, and active agents, as well as a wide range of ratios for the components. Although the present invention is described in considerable detail as to certain preferred versions of preparations and uses, other versions and uses are possible. Even though the formulations have been described for use to treat plants, the active agents may be used in other applications. For example, the use of the penetrants and/or carriers described in this invention (e.g., biosurfactants) can be used to deliver essential minerals, nutrients, and vitamins for humans and animals. Biosurfactant-nutrient complexes can increase the assimilation and delivery of nutrients for humans and animals. In addition, the penetrants can be used to deliver drugs commonly used in the treatment of human diseases such as cancer.

According to some embodiments of the invention, the production of fermentation broth or the microbial metabolites containing the microbial biosurfactant may be used without extraction or purification. If desired, extraction and purification of the biosurfactants can be easily achieved using standard extraction techniques described in the literature.

Additionally, by mixing the penetrant/carrier with the active substance(s), a lower dose is required to achieve the same therapeutic or nutritional value. Therefore, in another embodiment of the invention, the amount of active substances used in attaining the maximum nutritional and therapeutic effects is reduced. As such, this lowers or abolishes some or all the undesirable side effects associated with higher doses such as liver toxicity in humans or animals or phytotoxicity in plants.

Every year many drugs are rejected or taken off the market owing to their toxicity. The penetrants/carriers disclosed herein can be used to reformulate many such drugs, thereby reducing their toxicity by reducing the dose that is needed to achieve the same therapeutic or nutritional value, which can prevent the use of such drugs from being discontinued.

In one embodiment, the biosurfactant, such as the rhamnolipid, can be used as active agents to control pests, especially for plants and animals. Studies showed excellent success in treating the following pests: insects, mites, nematodes, moss, algae, amoeba, and parasites using rhamnolipids as the active agent. Also, the addition of an oil, such as a natural oil, to the biosurfactants greatly amplifies the efficacy of the biosurfactants. For instance, weed control by rhamnolipids is not very effective unless you use high amounts of the rhamnolipid, which can be cost prohibitive. However, formulating an oil with rhamnolipids makes the biosurfactant more potent, especially against small weeds and other pests. More particularly, the combination of a natural oil and a biosurfactant, such as a rhamnolipid, is effective in controlling insects (e.g., ants and grasshoppers) and nematodes. Also, the formulations of rhamnolipid with oils, such as natural oils enhances the efficacy of the biosurfactant against various fungi.

In one embodiment, a biosurfactant, such as a rhamnolipid can be used as a general preservative. Accordingly, the biosurfactant can be used as a preservative for tree cuttings, plant cuttings, flower cuttings, food, oils, cosmetics, beauty products, shampoos, cleaners, soaps, detergents, and plant nutrients, especially organic based compositions. For example, rhamnolipid contained within an oil or nutrients formulation can prevent microbial growth.

In one embodiment, a biosurfactant, such as a rhamnolipid can be used to treat and/or prevent various animal diseases. Examples of diseases that biosurfactants can be used against include whirling disease on fish caused by amoeba, hoof disease such as foot rot on cattle/pigs, and others.

EXAMPLES

The following examples, studies and illustrations should not be construed as limiting, and are presented for illustration purposes only.

Example 1

A 75% acephate solid formulation is prepared with 25 grams polyethylene glycol (PEG) and 75 grams acephate. Twenty-five grams mixture of Polyethylene glycol 1450 and 8000 was melted at 75° C. Seventy-five grams acephate was added to the premelted PEG with stifling for ten minutes. The material was then poured into molds to yield capsules with 0.75 grams acephate active ingredient per capsule.

Example 2

A 75% acephate slow release formulation is prepared with 15 grams MSM, 10 grams stearic acid, and 75 grams acephate.

Example 3

A 75% acephate solid formulation is prepared by mixing 25 grams MSM and 75 grams acephate. The mixture is pressed using a tablet press to yield tablets containing 0.75 grams acephate active ingredient per tablet.

Example 4

A homogeneous 75% acephate solid formulation is prepared with 1.5 grams rhamnolipid (or MSM), 1 gram cellulose, and 7.5 grams acephate.

Example 5

A 97% acephate solid formulation is prepared by mixing 97 grams acephate and 3 grams polyvinyl pyrrolidone. The material is pressed into tablets. If desired, the prepared tablets are encapsulated within a gelatin capsules or coated with polyvinyl alcohol.

Example 6

A 50% acephate liquid formulation is prepared with 1 gram rhamnolipid, 5 grams acephate and 4 grams water.

Example 7

A 25% acephate gel formulation is prepared with 2.5 grams glycerol, 0.5 grams DMSO, 4 grams polyethylene glycol 4000, 0.5 grams sodium stearate, and 2.5 grams acephate.

Example 8

A homogeneous 75% acephate formulation is prepared with 10 grams MSM, 5 grams rhamnolipid, 10 grams cellulose, and 75 grams acephate.

Example 9

A 25% imidacloprid liquid formulation is prepared with 7.5 grams DMSO and 2.5 grams imidacloprid.

Example 10

A 15% imidacloprid gel formulation is prepared with 8.3 grams DMSO, 0.2 grams cellulose, and 1.5 grams imidacloprid.

Example 11

A 20% imidacloprid formulation is prepared with 80 grams MSM and 20 grams imidacloprid. Solid MSM granules were melted at a temperature of 120° C. Twenty grams imidacloprid was added and stirred in the premelted MSM till the imidacloprid totally dissolved. The melted composition was poured into molds to yield capsules containing 0.20 grams imidacloprid per capsule.

Example 12

A homogeneous 25% Imidacloprid solid formulation is prepared with 3 grams Polyethylene glycol 1450, 1 gram DMSO, 3.5 grams MSM and 2.5 grams Imidacloprid.

Example 13

A 25% Imidacloprid solid formulation is prepared with 6.5 grams sorbitol, 1 gram rhamnolipid, and 2.5 grams Imidacloprid.

Example 14

A 25% Imidacloprid solid formulation is prepared with 6.5 grams MSM, 1 gram rhamnolipid, and 2.5 grams Imidacloprid.

Example 15

A 20% Imidacloprid formulation is prepared with 3 grams glycerol, 4 grams polyethylene glycol 4000, 0.5 grams sodium stearate, and 2 grams imidacloprid.

Example 16

A 10% Abamectin liquid formulation is prepared with 7.5 grams DMSO, 1.5 grams glycerol and 1 gram Abamectin.

Example 17

A homogeneous 10% Abamectin solid formulation is prepared with 3 grams ethylcellulose, 1 gram rhamnolipid, 5 grams MSM, and 1 gram Abamectin.

Example 18

A 10% rhamnolipid solid formulation is prepared with 9 grams MSM and 1 gram rhamnolipid

Example 19

A homogeneous 20% rhamnolipid solid formulation is prepared with 40 grams starch, 40 grams cellulose, and 80 grams rhamnolipid (25% strength). The material was dried at 70 degrees Celsius for 24 hours. The dry formulation was pressed using a tablet press to yield capsules containing 0.2 grams rhamnolipid.

Example 20

A homogeneous 10% slow release rhamnolipid formulation was prepared by mixing 50 grams of the mixture of example 19 with pre-melted 40 grams PEG 8000 and 10 grams myristic acid. The material was mixed well while maintained at 75 degrees Celsius. The final formulation is poured into molds.

Example 21

A 25% Thiamethoxan formulation is prepared with 7.5 grams MSM and 2.5 grams Thiamethoxan.

Example 22

A 70% potassium phosphite solid formulation is prepared with 3 grams sorbitol and 7 grams potassium phosphite.

Example 23

A 70% potassium phosphite solid formulation is prepared with 20 grams starch, 10 grams rhamnolipid and 70 grams potassium phosphite. The solid formulation is pressed into tablets.

Example 24

A 70% potassium phosphite solid slow release formulation is prepared with 10 grams stearic acid, 20 grams MSM, and 70 grams potassium phosphite.

Example 25

A 50% potassium phosphite liquid formulation is prepared using 50 grams potassium phosphite, 5 grams rhamnolipids, and 45 grams water.

Example 26

A dry mixture of NPK fertilizer with micronutrients is prepared using urea, ammonium nitrate, ammonium phosphate, potassium nitrate, calcium and magnesium chloride, and iron, manganese, zinc, and copper sulfate, and sodium borate. Half of the final blend was mixed with dry rhamnolipid (example 19) to yield a homogeneous formulation with the following analysis: 5-5-5 plus 0.2% Ca, 0.2% Mg, 0.1% Mn, 0.1% Fe, 0.1% Zn, 0.02% Cu, and 0.015% B. The final concentration of the rhamnolipid in the mix was about 12.5%. The other half was mixed with starch instead of rhamnolipid to yield the same concentration of nutrients in both blends. The mixtures were used to treat cabbage and tomato plants to determine yield and leaf tissues elemental analysis.

Example 27

A mixture of NPK was prepared in liquid formulation. Gluconate/citric acid buffer was used to maintain the blend at pH of 4.5-5 units. The final concentrations of the nutrients were similar to the analysis in the dry fertilizer formulation of Example 26. The final formulations contained 0 or 10% rhamnolipid concentration. The liquid mixtures were diluted 100 or 200 times and used to treat cabbage and tomatoes leaves.

In all experiments, whether the material was applied to a soil or leaf, the presence of rhamnolipid and/or biosurfactant in the nutrient mix was associated with enhanced plant growth and improved the uptake of most nutrients.

Example 28

A slow release dry formulation was prepared using the same ingredients as Example 26. Liquid rhamnolipid broth at 10% rhamnolipid concentration was intermittently sprayed on the fertilizer blend and gradually dried at 60° degrees Celsius. Starch was sprinkled on the mix to prevent the material from clumping. The final mixture of the blend contained about 2.5% rhamnolipid concentration as coating.

Example 29

A homogeneous gel formulation was prepared by mixing 50 grams of rhamnolipid solution (25% strength) and 5 grams DMSO in 50 grams of crosslinked swellable polyacrylamide granules. Rhamnolipid solution was totally impregnated in the granules in less than 20 minutes. The material was dried in the oven at 70 degrees Celsius. While the gel may be in certain applications, it is preferable to be in a dry form. The material may be used to treat pathogens such as fungi and nematodes. For soil, root flares, and tree injection applications, it is preferable to impregnate pre-molded polyacrylamide spikes with the active agent, such as rhamnolipid. The spikes can be dried to facilitate application and to increase effectiveness in soil applications.

Example 30

Citrus leafminer is a serious problem for citrus growers in Florida, Australia, and the Mediterranean countries. It attacks all varieties of citrus, but grapefruit, lemon and lime are more susceptible to infestation than other citrus varieties. Leafminers have a short developmental time and as many as 6-13 generations per year can be expected depending on foliage flushing cycles, nitrogen fertility, humidity, and temperature. The hatched larvae of citrus leafminer form serpentine mines in leaves and occasionally in the citrus fruit. Pupation occurs in folds on the edges of leaves. Leafminer larva is characterized by a central line of frass and is protected within the leaf. Infestation levels of up to 20 miners per leaf are common. Like borers, leafminer is not easily controlled by insecticidal spray.

Treatments were started at the beginning of the first foliage flush. Using formulations of Examples 1, 3, and 10, ten and twenty year old citrus (lemons, grapefruit, oranges) trees were treated, which were susceptible to natural infestation with the citrus miner. Each treatment consisted of four trees. Each of the two-year old seedlings was treated with two tablets inserted in the soil. Thirty leaves were collected from each treatment and the mines were counted. Qualitative measurement of the severity of infestation was observed. Each of the older trees was treated with three tablets inserted in the trunk at equal spacing. The trees were observed during two new growth flushes over two months period, and the results are set forth in Table 2.

TABLE 2 EFFECT OF ACEPHATE AND IMIDACLOPRID FORMULATIONS ON INFESTATION CITRUS TREES WITH CITRUS LEAFMINER. Treatments Time (days Control Example 1 Example 3 Example 10 after treatment) Average leaf damage area (%) 30 63 27 6 18 60 72 36 21 12

As seed in Table 2, the acephate formulation of Example 3, with the penetrant MSM, was the fastest and most effective treatment. Almost all infestation symptoms were eliminated in the presence of MSM. Imidacloprid formulation (Example 10) with MSM was also effective and had a longer residual activity. It was also observed that the treated trees with the formulation of Example 1 had inconsistent control on some branches. Some branches were more infested than the other branches on the four treated trees. While the physical processes that yielded these results are not critical to the understanding or use of the invention, it is believed that the presence of the penetrant has either improved the translocation of the pesticides throughout the trees or enhanced its penetration through the larvae and inaccessible leaf tissues or both.

Example 31

Aspen trees heavily infested with flat-head borers were treated using acephate (Examples 1, 2) and imidacloprid (Example 10) tablets. Each treatment consisted of six trees (about 7-8 inch trunk diameter) that were injected with three tablets per tree. The studies started at the first sign of borers infestation. Total borer activities and frass accumulation under the trees stopped within one month of the initiation of the studies. Both insecticidal treatments with MSM had the same effect. Acephate treatment without the penetrant MSM (Example 1) had less than 60 percent effectiveness as compared to the treatments with a penetrant. Control trees (no insecticide) were infested with borers for the whole season.

Example 32

Two Aspen trees infected with leaf spot fungal disease were each treated with four tablets containing phosphite (Example 23). All the new leaves exhibited a healthy growth and were free of fungal infection for the rest of the season.

Example 33

Into each 1-liter water bottle containing 0 or 500 ppm DMSO, a tablet containing 0.2 grams rhamnolipid (Example 19) was added. Ten-mosquitoes larvae were transferred into each of the bottles. Additional bottle contained ten-mosquitoes larvae in 1-liter water was used as control. Total death of the larva was observed in about 2 hours and 40 minutes in the bottle containing rhamnolipid alone. The presence of DMSO with the rhamnolipid caused death in less than 2 hours. No death was observed in the control treatment.

Example 34

A naturally infested ants mound was treated with four tablets of example 5. The mound was free of ants for more than two months after the treatment.

The processes, methods of use and examples of components listed in the invention are illustrative and not inclusive. The invention may be embodied in other specific forms without departing from its spirit or essential characteristics. The described embodiments are to be considered in all respects only as illustrative and not restrictive. The appended claims are presented to illustrate the embodiments of the invention disclosed herein. 

1. A method for controlling pests, the method comprising: obtaining a homogeneous penetrating composition comprising: at least one active agent in an effective amount to have an activity of controlling a pest so as to kill, disable, and/or immobilize the pest; and at least one biosurfactant penetrant selected from the group of glycolipids, rhamnolipids, lipopeptides, flavolipids, lipoproteins, phospholipids, lipopolysaccharide-protein complexes, or polysaccharide-protein-fatty acid complexes having the at least one active agent in the effective amount homogeneously dispersed therein, the at least one biosurfactant penetrant being present in an effective amount for carrying the at least one active agent in the effective amount into or through the pest in order to control the pest; and providing the homogeneous penetrating composition to a pest in an amount such that the pest is substantially controlled with the active agent.
 2. The method as in claim 1, further comprising at least one additional penetrant selected from the group consisting of aliphatic sulfones, acyclic sulfones, sulfones, sulfoxides, polyvinylpyrrolidone, and combinations thereof.
 3. The method as in claim 1, wherein the at least one active agent is selected from the group consisting of pesticides, elicitors, biopesticides, biopesticide byproducts, and combinations thereof.
 4. The method as in claim 3, further comprising at least one solubility controlling agent.
 5. The method as in claim 4, wherein the solubility controlling agent is selected from the group consisting of slow release cross-linked swellable gel, slow release cross-linked swellable polyacrylamide gel, wax, chitin, chitosan, C12-C20 fatty acid, myristic acid, stearic acid, palmitic acid, C12-C20 alcohol, lauryl alcohol, cetyl alcohol, myristyl alcohol, stearyl alcohol, amphiphilic esters of fatty acids, glycerol, monoester C12-C20 fatty acids, glyceryl monolaurate, glyceryl monopalmitate, glycerol esters of fatty acids, polyethylene monostearate, polypropylenemonopalmitate glycols, C12-C20 amines, lauryl amine, mystyl amine, stearyl amine, amide C12-C20 fatty acids, and combinations thereof.
 6. The method as in claim 3, wherein the at least one active agent is complexed or chelated with the at least one biosurfactant penetrant.
 7. The method as in claim 1, wherein the biosurfactant penetrant is selected from the group consisting of glycolipids, lipopeptides, flavolipids, rhamnolipids, lipoproteins, phospholipids, lipopolysaccharide-protein complexes, polysaccharide-protein-fatty acid complexes and combinations thereof.
 8. The method as in claim 1, wherein the biosurfactant penetrant is a glycolipid and the active agent is a pesticide.
 9. The method as in claim 1, wherein the composition is a liquid homogenous composition.
 10. The method as in claim 1, wherein the composition is a homogeneous solid, or paste composition.
 11. The method as in claim 1, comprising preparing the homogeneous penetrating composition, the preparing comprising one or more of the following: mixing for about 10 minutes; mixing under heat; compression molding the homogeneous composition; tabletting the homogeneous composition; pressing the homogeneous composition; extruding the homogeneous composition; injection molding the homogeneous composition; or liquefying the homogeneous composition.
 12. The method as in claim 1, wherein the biosurfactant is obtained from a microbe selected from the group of: Pseudomonas species; Flavobacterium species; Candida species; Rhodococcus species; or Arthrobacter species.
 13. The method of claim 1, further comprising cultivating a microbe so as to produce the biosurfactant.
 14. The method of claim 1, wherein the biosurfactant includes a rhamnolipid and/or a sophorlipid.
 15. The method of claim 1, wherein the pests are selected from fungi, nematodes, leafminers, citrus leafminers, borers, flat-head borers, leaf spot fungi, insects, mosquitoes, ants, eggs thereof, or larva thereof.
 16. A method for controlling pests, the method comprising: obtaining a homogeneous penetrating composition comprising: at least one active agent in a first effective amount to have an activity of controlling a pest so as to kill, disable, and/or immobilize the pest; and at least one biosurfactant penetrant selected from the group of glycolipids, rhamnolipids, lipopeptides, flavolipids, lipoproteins, phospholipids, lipopolysaccharide-protein complexes, or polysaccharide-protein-fatty acid complexes having the at least one active agent in the first effective amount homogeneously dispersed therein, the at least one biosurfactant penetrant being present in a second effective amount for carrying the at least one active agent in the effective amount into or through the pest in order to control the pest, wherein the first effective amount is larger than the second effective amount; and providing the homogeneous penetrating composition to a pest in an amount such that the pest is substantially controlled with the active agent.
 17. The method as in claim 16, wherein the biosurfactant penetrant is a glycolipid and the active agent is a pesticide.
 18. A method for controlling pests, the method comprising: obtaining a homogeneous penetrating composition comprising: at least one active agent in a first effective amount to have an activity of controlling a pest so as to kill, disable, and/or immobilize the pest; and at least one microbial biosurfactant penetrant obtained from a microbe and selected from the group of glycolipids, rhamnolipids, lipopeptides, or flavolipids, having the at least one active agent in the first effective amount homogeneously dispersed therein, the at least one biosurfactant penetrant being present in a second effective amount for carrying the at least one active agent in the effective amount into or through the pest in order to control the pest, wherein the first effective amount is larger than the second effective amount; providing the homogeneous penetrating composition to a pest in an amount such that the pest is substantially controlled with the active agent.
 19. The method as in claim 18, wherein the biosurfactant is obtained from a microbe selected from the group of: Pseudomonas species; Flavobacterium species; Candida species; Rhodococcus species; or Arthrobacter species.
 20. The method as in claim 18, wherein the biosurfactant penetrant is a glycolipid and the active agent is a pesticide. 